Lithiation Induced Hetero‐Superlattice Zn/ZnLi as Stable Anode for Aqueous Zinc‐Ion Batteries

Abstract Three dimensional (3D) framework structure is one of the most effective ways to achieve uniform zinc deposition and thus inhibit the Zn dendrites growth in working Zn metallic anode. A major challenge facing for the most commonly used 3D zincophilic hosts is that the zincophilic layer tends to peel off during repeatedly cycling, making it less stable. Herein, for the first time, a hetero‐superlattice Zn/ZnLi (HS−Zn/ZnLi) anode containing periodic arrangements of metallic Zn phase and zincophilic ZnLi phase at the nanoscale, is well designed and fabricated via electrochemical lithiation method. Based on binding energy and stripping energy calculation, and the operando optical observation of plating/stripping behaviors, the zincophilic ZnLi sites with a strong Zn adsorption ability in the interior of the 3D ZnLi framework structure can effectively guide uniform Zn nucleation and dendrite‐free zinc deposition, which significantly improves the cycling stability of the HS−Zn/ZnLi alloy (over 2800 h without a short‐circuit at 2 mA cm −2 ). More importantly, this strategy can be extended to HS−Zn/ZnNa and HS−Zn/ZnK anodes that are similar to the HS−Zn/ZnLi microstructure, also displaying significantly enhanced cycling performances in AZIBs. This study can provide a novel strategy to develop the dendrite‐free metal anodes with stable cycling performance.